Absrracr: By exploiting the selective hydrogen atom transfer reactions of glycine residues in small peptides, it is possible to utilise other amino acid residues as chiral auxiliaries in stereoselective synthesis. Alternatively, radical side-chain functionalisation of N-phthaloyl-substituted amino acid derivatives occurs without racemisation. The synthetic utility of the latter procedure is enhanced by the ability to use the phthaloyl group in subsequent reactions to remember the chirality of the amino acids.